Suspension-type polymerization process



United States Patent SUSPENSION-TYPE POLYIVIERIZATION PROCESS Walter G. May, Union, N. .L, and George L. Matheson, deceased, late of Summit, N. J., by The Summit Trust Co., executor, Summit, N. J., assignors to Esso Research and Engineering Company, a corporation of Delaware Application September 17, 1952, Serial No. 310,048

6 Claims. (Cl. 260-68315) This invention relates to an improved non-regenerative catalytic polymerization process in which olefin hydrocarbons are continuously polymerized by means of a solid polymerization catalyst suspended in fluid hydrocarbon. More particularly, it relates to a process in which olefins are polymerized to form high octane polymers boiling in the gasoline boiling range which are suitable as motor fuel blending agents and the like.

It is known in the art to suspend finely divided solid polymerization catalyst in dense fluid hydrocarbon and to contact an olefin to be polymerized with the agitated suspension under polymerization conditions. A particularly suitable method has been to maintain the catalyst in suspension by means of mechanical stirrers. This procedure also helps to maintain uniform reaction conditions throughout the zone and gives good top to bottom mixing of catalyst in the zone. This type of opera tion, however, presents mechanical difiiculties at high reaction pressures due to leakage of hydrocarbons through packing glands needed for the mechanical stirrers. Furthermore, severe mechanical agitation of the catalyst causes attrition thereof at a rapid rate resulting in high loss of catalyst due to entrainment with the product.

It has also been proposed to carry out a suspensiontype process of the above character by using a hindered settler reaction zone in which catalyst is maintained in suspension by upflow of the hydrocarbon feed. This type of operation presents difliculties in maintaining uniform mixing of the suspension and in preventing stratification of the catalyst. Indeed, such systems are operated such that stratification does occur, the coarser sizes of the catalyst settling to the bottom, the smaller sizes at the top, and here may be an interface existing between a lower dense catalyst phase and an upper solid free phase. It is a primary purpose of the present invention to provide a suspension-type polymerization process that overcomes some of these difiiculties without the necessity of using mechanical stirrers or other similar agitating devices.

In accordance with the present invention, a substantially uniform suspension of finely divided solid polymerization catalyst in fluid hydrocarbon is maintained throughout the reaction zone. Olefin feed is continuously passed upwardly through the suspension under polymerization conditions of pressure, temperature, contact time and the like. Effluent containing polymerized olefins and suspended catalyst is continuously Withdrawn from the top of the reaction zone, and solid catalyst is separated from the hydrocarbon in the efliuent by means of settling devices, cyclone separators or the like. The resulting substantially solid-free eifluent is divided into a product stream and a recycle stream.

At least a major portion of the recycle efliuent stream is introduced as at least one high velocity jetted stream at a lower intermediate point in the reaction zone, the direction of the flow of the jetted stream being substantially traverse to the flow of the olefin feed. The jetted stream causes turbulence and substantial mixing 2,761,889 Patented Sept. 4, 1956 of the suspension throughout the zone. The solid catalyst separated from the efiiuent stream is continuously introduced into the lower portion of the suspension within the reaction zone at a point above the olefin feed inlet whereby it is recirculated through the zone. The introduction of jetted recycle efiiuent and separated catalyst at these points in the system provides an effective means for obtaining thorough top to bottom mixing of the catalyst, minimizes Stratification of the catalyst within any specific portion of the reaction zone, and minimizes mechanical and attrition difliculties of the type encoun tered with mechanical stirrers.

In a further modification of the present invention, a minor portion of the recycled effluent stream is introduced into the bottom of the reaction zone, at a point below the introduction of the separated catalyst, and is passed upwardly through the suspension. Preferably, this stream is combined With the olefin feed and the mixture is introduced into the reaction zone. This modification is advantageous when the amount of olefin feed is insufificient to maintain the catalyst in suspension at the bottom portion of the reaction zone. Other advantages of the present process will become apparent from the following description taken in conjunction with Figures 1 and 2 which illustrate preferred embodiments of the invention.

Turning now to Figure 1, the numeral 11 designates a reaction zone containing a suspension of finely divided solid polymerization catalyst in fluid hydrocarbon. If desired, reaction zone 11 may be a jacketed reactor. Provision may be made for circulating a cooling medium through the jacket thereof for removing at least a portion of the exothermic heat of reaction formed during the polymerization process. This reaction zone is further provided with a bottom olefin feed inlet line 12 containing control valve 10 through which olefins are continuous- 1y introduced upwardly through the reaction zone. A distribution means 13, which may be a porous plate, a perforated plate, or the like, is provided in the bottom of reaction zone 11 above the olefin feed inlet. This distribution means permits a substantially uniform distribution of olefin feed throughout the cross sectional area of the reaction zone.

Zone 11 is also provided with a top efiiuent outlet line 14 which permits the withdrawal of efiiuent comprising suspended catalyst, polymerization products and unreacted olefins from the top portion of the suspension. Line 14 terminates in the upper portion of a separator 15, such as a conventional cyclone separator, wherein solids are removed from the hydrocarbon and settle by gravity downwardly through dip leg 16. Dip leg 16 fluidly connects the lower portion of separator 15 with the lower portion of the suspension reaction zone 11.

Separator 15 may consist of a plurality of cyclone separators, filters, bafiled settlers or the like, operating in series or parallel, it several are needed to efiect substantially complete separation of solid and fluid.

Substantially solid-free effiuent is Withdrawn from separator 15 through pipe 19. This efiluent is then divided into two streams, a portion of which is Withdrawn through branch line 20 containing valve 21 and is sent to a product recovery system. The amount of the product stream withdrawn will substantially balance the amount of fresh feed introduced into the system to maintain the pressure constant. The remainder of the solid-free effluent stream is passed through line 22 containing pump 23 and is recycled to the suspension in the reaction zone. At least a major portion of the recycled eiiluent passes through branch line 24 containing control valve 25. Line 24 connects with nozzle 26 which is horizontally positioned in the suspension. This nozzle is of sufficiently small outlet diameter to form a high velocity jetted 35; stream flowing traversely to the upward flow of the olefins. Obviously, line 24"may terminate in a plurality of nozzles extending into the suspension Withinthe reac- .1 1. on N zz e a reterahly, aqinlsiouarsllhe ra s ct onal. crater. e saa onjzau usus sn Q btaia.

n has! he oa ef r ozzle ho ldl sng it w fi u h. t he iett d u at tswil tnqt.crea sz u rlul yrl ddy naas onj ha aq e istie t mqstnt hau pa fi i rr r in e u p nsi n. 3 9 qt pnr abi t he a aly t Pa t o c ntz ius l or whi h esu t n. QI J Q -Z form distribution of th e particles.

A minor por i ot e' es e tfl en ma ift e irsi; pass through branch line 21 containing control ,va lye 2&

Line 27 fluidly connects withole eed h'ne When the amount of olefin feed,introducedjhrough hne 12 j1s insufiicient to maintain catalystin suspension the bottom parrot-the reaction zone, thisnunor amount is introduced with the olefin feed to'provide the add tionalinsures; good top to bottom mixing and uniform utiliz a tionof the catalyst-.

Spent catalyst is continuously 'or intermittently withdrawn fro m the reaction zone by means of line 29 containing-controlf valve 30. This spentcatalyst isconyeniently withdrawn asasuspension andmay be disposedpf:

A constantcatalyst inventory is maintained within the system by'introducingmake-up catalyst through line 31- containing-=valve 32, the make-up catalyst being substantially equivalent to. the amount lost from the system by entrainment or by withdrawal; through line 29; The make-up catalyst mayconyenientlybe introduced as a suspension-of finely-diyidede catalystii hydroparbon, such asthe polymer recovered from. thegpro'duct; stream, or

other suitablehydrocarbon material; 'Freshcatalyst; is; preferably introduced into-thereaction -zone below the pointof thejetted recycle streams, p

The positioning of thenozzle inletsisillustrated in Figure.2 which-represents a cross section. of the reaction zone. Nozzle 26: is directed toward thecenter of-'the reaction zone. A unidirectional flow offthis; type, pro

viding the jetted stream is-of extremely high velocity,

zgenesa.

sulficient distance in the suspension to give the desired degree of agitation and turbulence. Y

The amount of hydrocarbon eflluent recycle must be suflficient to maintain the catalyst in suspension and to furnish the desired degree of mixing. As a general rule, it will be necessary to maintain agatio of recycle efiiuent to olefin feed above about 30:1, preferably in the range of; about, 100:1; to 499:1; least a maior portionof this reQyclestr earnis introduged,

s. he-high el si v'i t Ge e a ly.a t. %i. t

elo he: Poi o ntro u t on. of. e eweled;- atell vto prevent the catalyst from setting in the bottom portion ofthezone. 7

It is p utlbat lids e' h tau ell completely removed from the hydrocarbon efiluent before it is re-' cycled to the suspension. If appreciable solids are pres ent this. m. hey W @I i Pl lllRil nwations nd. rm e iHQ IQdF. aaalesul sd or. ett n the. efllfle'nt- 9. ther hands. he. epa ateda id.- recysledwlidsmay cl de dtnusrt ydrosar oa.

it is most convenie'nt to use separatingdevicespositioned thoria, dehydratedactivated alumina, copper pyrpphdg phate and the like. While the sizeoffthe catalyst isnot' particularly critical' sizes in the range of about 29 to 200 mesh or even finer may be employed. I

The fluidhydrocarbon phase in which the. catalyst 'is suspended-1 may be a liquid phase, a vapor .phase 'or a; critical'phaseat pressuresaboy e the critical'for the hydrocarbons 'inthe reaction zone. Although; the process is operable; at fairly lowreaction pressure, 'it hasparticularapplication to operations with pr 'ess ures above about 400 to 5001). s. i; g, atwhich th hydrocarbons are fairly dense, since-difiiculties'in keeping the catalystguniforrnly suspended are more pronounced at; the higher pressuresf Pressures above about 909 p. s. i. g. are, particularly willz provide the desired circulation and mixing; The I nozzles 26!- pointin a more or lessopposedtangentialdirection toward the sides-ofthe reaction zone to provide turbulence. The use of 'onlyone tangentiallydirectednozzle. or any other such nozzle arrangement should-be avoided if a swirl-ing action on thesuspension results.

intermediate portion refers to positions above the olefin d inlet d. ow he rt a sai er of! helea t zoile- The zz es. ho ld e. po itioned & bi e the jetted streams do notinterfere withthe free flow. Qf. cata- 3 ro d p. e .6 fe y he nozz e a po tioned above, the dip leg outlet. Howeyer, the dip; leg

may be positioned in theis ide of the r eaction zone oppo: site the. nozzle inletaorthe, dip leg qutlet-rnay be; bafli'ed h 9 et de fhe nozz esare elowhep legoutlet. I V H In; orderto. create the. desired. degree. ofturbulence,

the diameter Off the. jetted streams usually be less velocit'yethat is qu r o. ca se h m. o. penetra e a The relativev v desirable when polymerizing riormallyfgaseous olef ns in'; order to obtain a-critical-phase-operatioii and'tq achieve high olefin conversions.- V e The temperature withinthe reaction zone is not'panticularly critical and will depend to a' large extent on, thetypeof catalyst being usedan d theparticular olefin being, polymerized: Temperatures' within the range qrabout 250 to 600 F. are generally suitable for most; conventional solid polymerization catalysts when produc; ingtdimers. and: trimers; boiling in thegasoline-boiling range from normally gaseous-oleiinson-when producin tetramers: or higher polymers. useful as chernicalinter? mediates.

The olefinfeeds 'i useful in the. present inventioninclude. the normally gaseous olefins; such as ethylene,

propylene, butylenes, and thehigher olefins such-Las As mentioned heretofore, at

To illustrate a typical operation, a C4 hydrocarbon feed containing about 50% olefin is employed as feed stock. The reaction zone is maintained at about 450 F. and 1000 p. s. i. g. A suspension consisting of finely divided solid catalyst comprising 80% phosphoric acid deposited on silica gel in fluid hydrocarbon comprising olefin feed and polymerization products is maintained throughout the reaction zone. The catalyst concentration in the suspension is maintained at about lbs./cu. ft, the catalyst itself having a bulk density of about 60 lbs/cu. ft. Olefin feed is introduced into the bottom of the reactor at a rate of 1 gallon/hour/pound of catalyst, the size of the reactor being such that the superficial velocity of fresh olefin feed is about 0.001 ft./sec. The Withdrawn efliuent is separated into its solid particle and hydrocarbon components. The amount of product stream Withdrawn from the system is controlled so that the ratio of recycle efiluent to feed, on a volume basis, is about 285:1. The major portion of the recycle efiiuent is introduced as high velocity jets as heretofore described, While a minor portion thereof is introduced in admixture with the olefin feed. This results in a superficial velocity of fluid through the reaction zone of about 0.3 ft./sec. which is sufiicient to maintain the catalyst in suspension and to obtain turbulence and mixing Within the reaction zone. The separated catalyst is continuously recycled to the lower portion of the sus pension.

While the above operation has been described in connection with only one reaction zone, it will be obvious to the skilled workmen that two or more such zones may be operated in series in order to obtain high olefin conversion or to obtain other process modifications. The process of the present invention may also be employed in conjunction with other conventional types of polymerization operations, such as a fixed bed unit operating in series with a reaction zone of the type described.

Since conventional solid polymerization catalysts, such as phosphoric acid deposited on kieselguhr, tend to agglomerate due to the formation of sticky deposits thereon after prolonged operation periods, it may be desirable to include in the suspension a small amount, such as about5% to 30% based on the catalyst, of a finely divided solid diluent. Solid diluents, particularly adsorbents such as silica gel, alumina, activated carbon and the like, when maintained in cosuspension with the catalyst, substantially eliminate such agglomeration difliculties. The adsorbent will, of course, be withdrawn in the efiluent suspension and will be separated in the cyclone separator or other separating devices and returned to the reaction zone along with the catalyst.

It will also be obvious to the skilled workman that certain types of polymerization catalysts, such as solid phosphoric acid catalysts, will require the periodic or continual introduction of a small amount of water of hydration into the reaction zone in order to maintain maximum catalyst activity. This Water may be introduced with the olefin feed or may be injected from another source into the reaction zone. Generally the amount of Water maintained in the reaction zone is such that its partial pressure will substantially balance the vapor pressure of the catalyst under reaction conditions.

What is claimed is:

l. A continuous non-regenerative catalytic process for polymerizing olefin hydrocarbons which comprises providing a reaction zone including a bottom olefin feed inlet and a top efiluent outlet, maintaining throughout said zone a suspension of finely divided solid polymerization catalyst in fluid hydrocarbon, continuously passing olefin feed upwardly through said suspension at polymerization conditions, continuously withdrawing eifiuent suspension from the upper part of said zone and separating solids from said efiluent suspension, dividing the resulting substantially solid-free efi luent into a product stream and recycle stream, introducing said recycle stream into said suspension, at least a major portion of which is introduced as at least one jetted stream at a lower intermediate point in said reaction zone, the direction of flow of said jetted stream being substantially traverse to the flow of said olefin feed through said zone whereby substantial mixing of said suspension takes place, and introducing said separated solids into a lower portion of said suspension at a point intermediate said olefin feed inlet and point of introduction of said jetted stream whereby said catalyst is recirculated through said zone.

2. A process as in claim 1 wherein a minor portion of sa d recycle stream is introduced into said reaction zone With said olefin feed and is passed upwardly through said suspension.

3. A process as in claim 2 wherein said minor portion is at least 10% of said recycle stream.

4. A process as in claim 1 wherein the volume ratio of said recycle stream to said olefin feed is at least 30:1.

5. A process as in claim 4 wherein at least 10% of said recycle stream is introduced with said olefins into said reaction zone.

6. A process as in claim 1 wherein said jetted recycle stream is introduced into said suspension above the point at which said separated solids are introduced therein.

References Cited in the file of this patent UNITED STATES PATENTS 2,131,191 Roetheli et al Sept. 27, 1938 2,171,250 Archibald Aug. 29, 1939 2,436,595 Nicholson Feb. 24, 1948 2,571,262 Latchum Oct. 16, 1951 2,626,292 Gornowski Jan. 20, 1953 2,658,933 May et al. Nov. 10, 1953 

1. A CONTINOUS NON-REGENERATIVE CATALYTIC PROCESS FOR POLYMERIZING OLEFIN HYDROCARBONS WHICH COMPRISES PROVIDING A REACTION ZONE INCLUDING A BOTTOM OLEFIN FEED INLET AND A TOP EFFLUENT OUTLET, MAINTAINING THROUGHOUT SAID ZONE A SUSPENSION OF FINELY DIVIDE SOLID POLYMERIZATION CATALYST IN FLUID HYDROCARBON, CONTINUOUSLY PASSING OLEFIN FEED UPWARDLY THROUGH SAID SUSPENSION AT POLYMERZATION CONDITIONS, CONTINUOUSLY WITHDRAWING EFFLUENT SUSPENSION FROM THE UPPER PART OF SAID ZONE AND SEPARATING SOLIDS FROM SAID EFFLUENT SUSPENSION, DIVIDING THE RESULTING SUBSTANTIALLY SOLID-FREE EFFLUENT INTO A PRODUCT STREAM AND A RECYCLE STREAM, INTRODUCING SAID RECYCLE STREAM INTO SAID 